**DEECO Inc. 3404 Lake Woodard Road**  **Raleigh, NC 27604 (919) 250-0285 (ph); (919) 250-1835 (Fax)**  **www.deeco.com**

REPORT NO: **042110-2526**

PROJECT: **10-2526**

DATE: **May 7, 2010**

TYPE: 

## Emission Test Report

U.S. EPA Information Collection Request

for Hydrogen Chloride Emissions

from Portland Cement Manufacturing Facilities

Holcim (Texas) LP Midlothian, Texas

AUTHOR: **Scott Steinsberger, Ph.D.**

TEST DATE: **April 30, 2010**

FIELD TEAM: **Josh Fox, John Martin, and Scott Steinsberger**

PREPARED FOR: **Holcim (US), Inc. 201 Jones Road**  **Waltham, Massachusetts 02451 i**  TABLE OF CONTENTS
**Section Page** 

**1. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1** 

**2. SUMMARY OF RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5** 

**3. SAMPLING AND ANALYTICAL PROCEDURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7**  **3.1 EPA Method 1 and 2 - Stack Gas Volumetric Flow Rate Determination . . . . . . . 7 3.2 EPA Method 4 - Stack Gas Moisture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .**  **. . . . . 7 3.3 EPA Method 3A - Stack Gas Oxygen and Carbon Dioxide . . . . . . . . . . . . . . . . . 9**  **3.3.1 Gas Sampling System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9**  **3.3.2 Oxygen and Carbon Dioxide Monitor . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.3.3 Data Acquisition System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .**  **. . . . 10 3.3.4 Calibration Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .**  **. . . . . 10 3.4 EPA Method 321 - Stack Gas Hydrogen Chloride . . . . . . . . . . . . . . . . . . . . . . . 11**  **4. QA/QC PROCEDURES AND RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14**  **4.1 Sampling Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14**  **4.1.1 Manual Sampling Equipment Calibrations . . . . . . . . . . . . . . . . . . . . . . . 14**  **4.2 Analytical QA/QC Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15**  **Appendix A - Emission Summary Sheets Appendix B - Field Sampling Data Sheets**  **Appendix C - Continuous Emission Monitoring Results Appendix D - FTIR Data**  **Appendix E - Equipment Calibration Data Sheets and Calibration Gas Certifi cates of** 

**Analysis Appendix F - Test Participants** **ii** LIST OF TABLES **Table No. Page**  **TABLE 1.1 SUMMARY OF HYDROGEN CHLORIDE EMISSIONS; HOLCIM (TEX AS)** 

**LP MIDLOTHIAN, TEXAS FACILITY; APRIL 30, 2010 . . . . . . . . . . . . . . . . . 3 TABLE 1.2 SUMMARY OF SAMPLING AND ANALYTICAL PROTOCOLS FOR** 

**HOLCIM (TEXAS) LP MIDLOTHIAN, TEXAS FACILITY . . . . . . . . . . . . . . . 4**  **TABLE 2.1 HYDROGEN CHLORIDE EMISSION TEST RESULTS, HOLCIM (TEX AS)** 

**LP MIDLOTHIAN, TEXAS FACILITY; RAW MILL ON CONDITION; APRIL 30, 2010 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .**  **. . . . . . . 6 TABLE 2.2 HYDROGEN CHLORIDE EMISSION TEST RESULTS, HOLCIM (TEX**  **AS) LP**

**MIDLOTHIAN, TEXAS FACILITY; RAW MILL OFF CONDITION; APRIL 30, 2010 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .**  **. . . . . . . . . . 6 TABLE 3.1 HYDROGEN CHLORIDE ANALYTE SPIKING TEST RESULTS, HOLC**  **IM**

**(TEXAS) LP MIDLOTHIAN, TEXAS FACILITY; RAW MILL ON CONDITION; APRIL 30, 2010 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .**  **. . . 13 TABLE 3.2 HYDROGEN CHLORIDE ANALYTE SPIKING TEST RESULTS, HOLC**  **IM**

**(TEXAS) LP MIDLOTHIAN, TEXAS FACILITY; RAW MILL OFF CONDITION; APRIL 30, 2010 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .**  **. . . 13**

LIST OF FIGURE **Figure No. Page**  **Figure 3.1 Schematic of the Main Kiln stack. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8** **1** 

### 1. INTRODUCTION **The U.S. Environmental Protection Agency (EPA), Office of Air Qual ity Planning and**  **Standards (OAQPS) issued an Information Collection Request (ICR) t o Holcim (US), Inc (Holcim).**  **Under the authority of Section 114 of the Clean Air Act (CAA), the E PA requested information on**  **hydrogen chloride (HCl) emissions from nonhazardous waste-burning kilns at Portland cement**  **manufacturing facilities. The request was in response to comment s from Portland cement industry**  **members and its trade association to EPA’s proposal to amend t he national emission standards for**  **hazardous air pollutants for Portland cement manufacturing (74 FR 21136 (May 6, 2009)). Holcim retained DEECO Inc. (DEECO) to conduct the required emissi**  **ons testing. Testing for HCl was conducted in accordance with EPA Method 321 - Measurement**  **of Gaseous Hydrogen Chloride Emissions At Portland Cement Kilns by Fourier Transform**  **Infrared (FTIR) Spectroscopy. The Holcim facility in Midlothian, TX (1800 Dove Lane, Midlothian, TX 76065)**  **has been one of the Portland cement manufacturing facilities selected as**  **part of the ICR. Holcim operates a dry process kiln system at this facility.**  **The Midlothian Plant's Portland cement manufacturing process invol ves raw materials**  **acquisition and handling, kiln feed preparation, pyro-processing, and finis hed cement grinding and**  **loading. Each of the Midlothian Plant's Line 1 and Line 2 pyro-process ing systems consist of a four**  **stage preheated precalciner system (Emission Point Numbers [EPNs] 7 and 65). Both lines have a**  **bypass system to control the quantity of alkali and sulfur since t he nature of the raw materials**  **requires that alkali and sulfur be removed to control the quality of t he clinker. Water spray**  **conditioning towers designed to cool gases are located in the ducting b etween the preheaters and the**  **raw mills. When the mill systems are not operational, the sp ray towers protect the main baghouses**  **from high temperatures. The spray towers are not used when the mill systems ar e operational.**  **Testing was performed at the stack under two conditions, Raw Mill On and Raw Mil l Off,**  **on April 30 th**  **, 2010 Sampling was conducted by personnel from DEECO, Inc. of Raleig**  **h, North Carolina. Emission measurements were conducted simultaneously at the Main Ki**  **ln Stack for temperature, volumetric flow rate, dry gas molecular weight, moisture, and hydroge**  **n chloride. A summary of the sampling and analytical methods are presented in Table 1.2.**  **All questions regarding sampling and analytical data should be dir ected to Dr. Scott**  **Steinsberger of DEECO at (800) 733-3261. The field sampling was completed by Josh Fox, John**  **Martin, and Scott Steinsberger of DEECO. The remainder of this document summarizes the results, procedures**  **and quality control measures followed for this program. Section 2 contains tabulated a**  **ir emission results for each parameter of interest. Section 3 summarizes the air emi**  **ssion sampling and analytical procedures performed by DEECO, with a brief description and/or reference**  **to the applicable methodologies. Section 4 discusses the basic quality control elements in place**  **for this program to assure the collection of representative, accurate air emission data.** **2**

**The appendices provided in this document contain all of the necessary i nformation to verify**  **the reported results. Included as Appendices are: A - Emission S ummary Sheets; B - Field Sampling**  **Data Sheets; C - Continuous Emission Monitoring Results; D - FTIR Data; E - Equipment**  **Calibration Data Sheets and Calibration Gas Certificates of Analysis ; F - Test Participants.** **3**

TABLE 1.1 SUMMARY OF HYDROGEN CHLORIDE EMISSIONS; HOLC IM (TEXAS)

LP MIDLOTHIAN, TEXAS FACILITY; APRIL 30, 2010 Test Parameter Raw Mill On Raw Mill Off **Hydrogen Chloride Emissions (ppm at 7% oxygen) <0.42 <0.45** **4**TABLE 1.2 SUMMARY OF SAMPLING AND ANALYTICAL PROTOCOLSFOR HOLCIM (TEXAS) LP MIDLOTHIAN,TEXAS FACILITYLocation and Frequency Test Parameter Sampling MethodSampling Procedure Analysis Method Analysis Procedure**Kiln Main Stack Volumetric Flow Rate EPA Method 1 and 2** **with s-type pitot Velocity traverse with** **pitot for delta p EPA Method 2 Manometer and thermocouple** **readout Oxygen and** **Carbon Dioxide EPA Method 3A Continuous;** **extractive sample EPA Method 3A Paramagnetic for O** **2 and NDIR** **for CO 2** **Stack Gas Moisture EPA Method 4 Integrated sampling w ith** **condensation EPA Method 4 Gravimetric** **Hydrogen Chloride EPA Method 321 Continuous; extractive sample** **EPA Method 321 Fourier Transform Infrared (FTIR) Spectroscopy** **5** 

### 2. SUMMARY OF RESULTS

**Emissions sampling was conducted at the Holcim (Texas) LP fa cility located in Midlothian,**  **Texas. Sampling was conducted for stack gas HCl according to EPA Method 321. Concurrent ly,**  **sampling was conducted for stack gas volumetric flow (EPA Method 1 and 2), stack gas oxygen and**  **carbon dioxide (EPA Method 3A) and stack gas moisture (EPA Method 4). Testing was conducted**  **under two conditions; Raw Mill On and Raw Mill Off. The emissions results are summarized in Tables 3.1 and 3.2, respectively for**  **the Raw Mill On and Raw Mill Off conditions.** **6**

TABLE 2.1 HYDROGEN CHLORIDE EMISSION TEST RESULTS, HOL CIM (TEXAS)

LP MIDLOTHIAN, TEXAS FACILITY; RAW MILL ON CONDITION; APRIL 30, 2010 Test Parameter Run 1 Run 2 Run 3 **Average Time**  **08:35-09:35 10:05-11:05 11:32-12:32 ---- Stack Gas Temperature (**  E **F) 138 137 137 137 Stack Gas Moisture 18.3% 17.9% 17.9% 18.0%**  **Volumetric Flowrate actual cfm**  **dry standard cfm 467,100**  **332,800 464,400** 

**333,100 460,600** 

**330,300 464,100** 

**332,100 Oxygen Content 12.7% 12.8% 13.1% 12.9%**  **Hydrogen Chloride Emissions Concentration, ppm**  **by volume, wet basis Concentration, ppm**  **by volume, dry basis Concentration, ppm at 7% oxygen**  **<0.20 <0.24**  **<0.42 <0.20** 

**<0.24 <0.42**  **<0.20**

**<0.24 <0.43**  **<0.20**

**<0.24 <0.42** 
TABLE 2.2 HYDROGEN CHLORIDE EMISSION TEST RESULTS, HOLC IM (TEXAS)

LP MIDLOTHIAN, TEXAS FACILITY; RAW MILL OFF CONDITION ; APRIL 30, 2010 Test Parameter Run 4 Run 5 Run 6 **Average Time**  **15:02-16:02 16:30-17:30 17:58-18:58 ---- Stack Gas Temperature (**  E **F) 137 134 137 136 Stack Gas Moisture 17.2% 17.0% 17.9% 17.4%**  **Volumetric Flowrate actual cfm**  **dry standard cfm 450,200**  **325,500 449,600** 

**327.600 424,000** 

**304,100 441,300** 

**319,100 Oxygen Content 13.6% 13.7% 12.6% 13.3%**  **Hydrogen Chloride Emissions Concentration, ppm**  **by volume, wet basis Concentration, ppm**  **by volume, dry basis Concentration, ppm at 7% oxygen**  **<0.20 <0.24**  **<0.46 <0.20** 

**<0.24 <0.47**  **<0.20**

**<0.24 <0.41**  **<0.20**

**<0.24 <0.45** **7** 

### 3. SAMPLING AND ANALYTICAL PROCEDURES **Table 1.2 presents a summary of the overall sampling and analytica l protocols used for the**  **Information Collection Request (ICR) test program for the Line 2 Main Kiln stack at Holcim (Texas)**  **LP Midlothian, TX facility. All sampling and analytical meth ods employed for this test program**  **were performed in accordance with the procedures outlined in the R eference Test Methods contained**  **in the Code of Federal Regulations , Title 40, Part 60, Appendix A (40 CFR 60, Appendix A) and**  **40 CFR 63, Appendix A.**

3.1 EPA Method 1 and 2 - Stack Gas Volumetric Flow Rate Determination
**The Main Kiln stack was a round vertical duct with an inside dia meter of 164.063 inches.**  **The sampling ports were located on the Kiln stack over 7.5 duct diame ters above the nearest**  **disturbance, and more than two duct diameters below the stack dischar ge. This location meets the**  **minimum specifications for selection of a measurement site as outlined in EPA Method 1 (see**  **Appendix B). A schematic of the Main Kiln stack is shown in Figure 3.1. An 6-point velocity traverse in each of two perpendicular directions**  **was made at each sampling location using a type-S pitot tube in accordance with**  **EPA Method 2. Gas temperatures were measured using calibrated Type K thermocouples and digital readout devic**  **es. Dry gas molecular weight was determined using the oxygen and ca**  **rbon dioxide measurements following EPA Method 3A employing oxygen and carbon dioxi**  **de monitors. Stack gas moisture was measured in accordance with EPA Method 4 procedures.** 

3.2 EPA Method 4 - Stack Gas Moisture **The moisture content of the flue gas was determined using the met hodology described in**  **EPA Method 4. Based on this method, a known volume of particulate-free g as was pulled through**  **a chilled impinger train. The weight of each impinger was determined g ravimetrically before and**  **after sampling. The weight increase in each impinger was t hen related to the volume of gas sampled**  **to calculate the moisture content. During this test, the moisture content of the flue gas was determ**  **ined simultaneously with the Methods 3A and 321 sampling.** **9**

3.3 EPA Method 3A - Stack Gas Oxygen and Carbon Dioxide **A CEM system was used for determining the flue gas molecular weight and stack gas oxygen**  **content on the Main Kiln stack. The extractive monitors require that the effluent gas sample b**  **e filtered and maintained above condensation temperature, or conditioned to eliminate any possible i**  **nterference (i.e., water vapor and particulate matter), before being transported and delivered t**  **o each analyzer. All components of the sampling system which contact the sample are either of g**  **lass, stainless steel, or Teflon. A heated sampling probe with heated out-of-stack particulate filter, he**  **ated sample lines, an ice water-cooled condenser, a sample pump, and a gas distribution manifold are used to**  **deliver a representative sample of flue gas to each of the analyzers. Details of the**  **major components of the measurement system are presented below.**  3.3.1 Gas Sampling System **The gas sample was extracted from the stack through a glass lined probe and filter heated to**  **at least 356** E **F in an enclosure custom built for these test procedures. This heated enclosure was**  **equipped with heated glass-lined probe that allowed three traver se points on the line at 0.4, 1.2, and**  **2.0 meters from the stack wall be sampled equally during each test. The glass filter holder had a**  **teflon frit supporting a quartz fiber filter. Outflow of gas from the heated filter enclosure was**  **conveyed using a heat-traced Teflon sample line also maintained at least at 356**  E **F. The heated line was connected directly to the FTIR sample cell. A sample pump i**  **n a DEECO proprietary chiller type gas conditioner system was used to pull the gas sample t**  **hrough the system. The gas conditioner system was also used to remove moisture from the gas sample p**  **rior to introduction to the oxygen/carbon dioxide analyzer.**  3.3.2 Oxygen and Carbon Dioxide Monitor
**A CAI Model 200 O 2**  **/CO 2**  **analyzer was used to measure the oxygen and carbon dioxide concentrations. The oxygen concentrations are were measured using the**  **paramagnetic technique. Because of its sp3 electron orbital distribution, an oxygen mole**  **cule has an unpaired electron and hence displays a magnetic orientation. Since other elements that**  **display this magnetic phenomenon are not common gasses at normal temperatures, the paramagnet**  **ic measurement technique is virtually specific for oxygen. The sample gas flows through a detection ce**  **ll located in a very strong magnetic field. The magnetic nature of the oxygen causes the oxygen to move**  **to one side of the detection cell, inducing a pressure differential proportional to the oxygen concentration**  **in the detector cell. The analyzer measures this pressure differential, converts the pre**  **ssure differential to an electrical signal, and sends the results as output.**  **The carbon dioxide concentrations were measured using a single-beam photometr ic system**  **with a micro flow sensor detector. The micro flow detector is a sealed unit filled with carbon dioxide.**  **The instrument consists of an infrared light source, a chopper, a me asuring cell and a micro flow** **10**

**detector filled with carbon dioxide. The infrared light emitted b ackward is reflected by a reflecting**  **surface and is added to the infrared light emitted forward. Arrang ed between the infrared light source**  **and the measuring cell is a chopper blade which rotates to modulat e the infrared light beam at regular**  **frequency. The modulated infrared light beam thus formed passes thr ough the measuring cell filled**  **with a sample gas where the light energy is partially ab sorbed or attenuated before it reaches the front**  **chamber of the detector. Both the front and rear chambers of the de tector are filled with the gas**  **component to be measured. The infrared light energy is partiall y absorbed in the front chamber and**  **residual light is absorbed in the rear chamber, thereby incr easing the pressure in both chambers.**  **Since the detector is designed to produce a pressure difference b etween the front and rear chambers,**  **a slight gas flow is produced through a path connecting these chambe rs with each other. This slight**  **flow is converted into an AC electrical signal by a micro flow sensor.** 3.3.3 Data Acquisition System **Data were recorded on two separate devices. A hard copy was o btained using a Molytek 2702**  **strip chart recorder. Data was also recorded to the hard disk of an IBM compatible computer utilizing**  **the serial output of the Molytek recorder in conjunction with custom s oftware developed by DEECO**  **Engineers. Data for each of the analyzers was sampled each t wo seconds with a one minute average**  **being written to disk. Data was further averaged over the test period and corrected for calibration**  **error and drift using a spreadsheet program.**

3.3.4 Calibration Procedures **Calibration procedures were performed in accordance with EPA me thodology. Analyzers**  **were calibrated before and after each test and a calibration check was done between each test run.**  **The pretest calibrations consisted of the following steps:**

C **Internal (direct) calibration of each analyzer to adjust calibrati on and**  **check linearity.**

C **External (through the entire sampling system) calibration to c heck the**  **system bias on zero and span gases. The post test calibration consisted of an external system bias calibr**  **ation check Each analyzer was calibrated using a certified zero and span**  **(mid or high range) gas. Zero and span gases were directed to each analyzer through the appropr**  **iate plumbing, the calibration gas flow rates were adjusted to the correct flow rate and the analyzer w**  **as adjusted with the appropriate span pot.**  **After the analyzer was properly adjusted the linearity wa s checked using a low and high range**  **calibration gas. The maximum allowable limit for linearity is 2% of the analyzer range. All analyzers** **11**

**were shown to be linear within these limits. The external calibration bias check was performed by placing the CE**  **M system in sampling mode and injecting a zero and span gas into the sample line at the**  **probe exit. This check shows if there is any sampling system related bias, and also serves a**  **s a check of the integrity of the sample line.**  **DEECO used EPA Protocol and/or ±2% NIST Traceable gases f or calibration as required by the**  **various reference methods employed in this test program. Calib ration gases were selected from**  **previous experience with similar sources and/or from information o btained from the facility engineer**  **prior to sampling. In some cases if the gases that were se lected were out of the optimum range of**  **operation then no significant impact of data quality is expecte d due to the linear nature of the**  **analyzers that were used. No audit gases were available from federal or state agency.**  **At the completion of the pretest calibration routine, the CEM sy stem was ready for operation.**  **No further adjustments of sample flow rates, analyzer zero or span adjustments, or other critical CEM**  **operating parameters were made until testing and post test calibra tion were complete.**  **At the completion for each test run, calibration gases were used to check betwe en test runs.**  **A zero and the upscale calibration gas closest to the actual emission concentrations were used for the**  **pretest and post test calibrations.** 3.4 EPA Method 321 - Stack Gas Hydrogen Chloride **The sampling system described above was used to convey the gas s ample to the FTIR sample**  **cells. The FTIR sample cell was maintained at 356** E **F. The sample cell was connected to a MIDAC Corporation I-series Fourier Transform Infrared Spectrometer and Detect**  **or. The FTIR spectrometer measures vapor phase organic or inorganic**  **compounds which absorb energy in the mid-infrared spectral region, about 400 to 4000 cm**  **-1 (25 to 2.5 μm). Continuous**  **measurement is made by matching sample absorbance bands with bands in reference spectra, and**  **comparing sample band intensities with reference band intensities. The principle limitation to FTIR spectroscopy are the pres**  **ence of interfering compounds that also absorb energy in the mid-infrared spectral region. In a c**  **ement kiln stack gas matrix, water vapor (H**  **2 O) and carbon dioxide (CO**  **2 ) are the primary interferents that must be incorporated**  **into the identification and quantitation method.**  **The FTIR software performs the computation for a single compou nd by subtracting all the**  **other compounds (interferants and target) from the absorbance spe ctra and quantifies the single**  **compound based on the remain absorbance. The FTIR software provides a Standard Error** **12**

**Calculation (SEC) value that is an indication of how well the identi fication and quantitation has been**  **performed. A high SEC indicates that other interferants have not b een accounted for in the analysis**  **method, and a low SEC is indicative of greater confidence measurement. The instrument was operated with a resolution of 0.5 cm**  **-1 with 4x zero filling. Beer-Norton**  **Medium apodization was used with amplitude phase correction. Five ana lytical regions were used for**  **HCl; 2748.85 - 2754.20 cm -1**  **, 2772.80 - 2776.80 cm -1**  **, 2795.80 - 2800.20 cm -1**  **, 2818.80 - 2822.7 cm -1**  **, 2840.8 - 2845.7 cm**  **-1 , 2962.50 - 2964.0 cm**  **-1 , and 2997.0 - 2998.60 cm**  **-1 . These regions were found**  **to provide the lowest SEC values for this stack gas matrix. With this system at the 0.2 ppm detection limit required in the ICR, a M**  **aximum Analytical Uncertainty (MAU) of 0.15 ppm at cell conditions was calculated.**  **The ICR request that the detection limit be calculated according to Method 321. However, Method 321 does**  **not have provisions for calculating a detection limit. The method has the analyst sp**  **ecify the detection limit and then determine if the data quality of the analytical system meets**  **calculated criteria based on the desired detection limit. The MAU of 0.15 ppm is less than the 0.2 ppm required**  **detection limit, indicating that the FTIR system is suitable for measurement at this level.**  **Analyte spiking was conducted before and after each sampling run a ccording to Method 321.**  **The results are summarized in Tables 3.1 and 3.2. All analyte s pike recoveries were within the**  **required 70-130% and the pre and post test CTS calibration checks w ere within the 5% required .**  **It was apparent that higher spike recoveries were obtained with higher level s of native HCl.** **13**

TABLE 3.1 HYDROGEN CHLORIDE ANALYTE SPIKING TEST RESU LTS, HOLCIM

(TEXAS) LP MIDLOTHIAN, TEXAS FACILITY; RAW MILL ON CONDITION; APRIL 30, 2010 Test Parameter Pre Run 1 Post Run 1 Post Run 2 Post Run 3 **Time 08:03-08:27 09:36-10:01 11:06-11:28 13:34-13:58 HCl Spike Direct (ppm)**  **20.47 SF6 Tracer Direct (ppm)**  **10.90 Total HCl (spike plus native ppm) 2.250 1.862 1.736 1.6**  **74 Average Native HCl (ppm) 0.526 0.001 0.031 0.000**  **SF6 Tracer Diluted (ppm) 1.084 1.009 0.999 0.964 HCl Analyte Spike Recovery 87.4% 98.3% 91.1% 92.6%**  **Ethylene CTS Error 0.45% -0.07% -0.37% -0.65%**

TABLE 3.2 HYDROGEN CHLORIDE ANALYTE SPIKING TEST RESU LTS, HOLCIM

(TEXAS) LP MIDLOTHIAN, TEXAS FACILITY; RAW MILL OFF CONDITION; APRIL 30, 2010 Test Parameter Pre Run 4 Post Run 4 Post Run 5 Post Run 6 **Time 14:33-14:54 16:04-16:26 17:31-17:54 18:56-19:15 HCl Spike Direct (ppm)**  **20.47 SF6 Tracer Direct (ppm)**  **10.90 Total HCl (spike plus native ppm) 1.587 1.578 1.437 1.4**  **32 Average Native HCl (ppm) 0.000 0.000 0.000 0.000**  **SF6 Tracer Diluted (ppm) 0.988 0.983 0.976 0.985 HCl Analyte Spike Recovery 85.6% 85.6% 78.5% 77.5%**  **Ethylene CTS Error 0.33% -0.07% -0.08% 0.15% 14**  

### 4. QA/QC PROCEDURES AND RESULTS **The objective of a quality assurance/quality control (QA/QC) prog ram is to assure that the**  **precision and accuracy of all environmental data generated by DEE CO for clients are commensurate**  **with data quality objectives (DQO's). DQO's are based on a c ommon understanding of the intended**  **end use(s) of the data, the measurement process, and the availabili ty of resources. Once DQO's are**  **established, formally or informally, QC protocol can be defined for the measur ements.**  **In this project, the final data user will be Holcim. The data quality objec tives in this project**  **are to generate scientifically sound data to be used for compliance purposes**

**.**
4.1 Sampling Equipment **All of the sampling equipment used was calibrated according to t he procedures outlined in the**  **Quality Assurance Handbook for Air Pollution Measurement Systems , Volume III, EPA-600/4-77-**  **027b.** 4.1.1 Manual Sampling Equipment Calibrations **For sampling Methods 1, 2, and 4 the procedures and equipment used to measure st ack gas**  **velocity and temperature measurements and the metering system used to maintain constant rate**  **sampling conditions and to determine the sample gas volume were su bjected to pretest and posttest**  **calibrations and/or inspections as required by the appropriate EPA methods**

**.** Barometer **- Barometric pressure values were obtained from a calibra ted barometer, verified by**  **phone call to a local airport, and corrected for elevation to sampl e port level (0.01 inches Hg per 10**  **ft. elevation).**

Pitot Tubes **- Each pitot tube used in sampling meets the design specifi cations for type-S pitot tubes**  **in EPA Method 2. Therefore, a maximum value baseline coefficient (C**  **p ) of 0.84 is assigned to each**  **pitot tube. Calibration by the manufacturer for pitot face-o pening alignment included measuring the**  **external tubing diameter (dimension D t**  **), the base-to-opening plane distance (dimensions P a**  **and P b**  **), and the face opening misalignment angles, with all terms as de**  **scribed in EPA Method 2. Pitot tubes were visually inspected for structural integrity at the completion of each**  **test. Inspection sheets for pitot tubes are included in Appendix E.**  Calibration Meter and Metering System **- The secondary reference meter equipment arrangement for calibration is shown in Figure 5.7 of EPA Method 5. The prescrib**  **ed procedures were followed. A wet test meter with a 1 ft**  **3 /rev capacity and +**  **1 percent accuracy is used as the primary calibrant. The dry gas meter's pump is run for a minimum of 5 minutes at a**  **flow rate of 0.35 cfm to condition the interior surface of the wet test meter. Leak checks are**  **performed and if satisfactory, triplicate runs at each of no less than five different flow rates are done. A**  **calibration curve is prepared and the meter is recalibrated after 200 hours of operation or annually, whichever comes fi**  **rst. 15** 

**The calibration set-up for the dry gas metering system usi ng the secondary reference meter**  **in lieu of the wet test meter is given in Figure 5.5 of EPA Method 5. A leak che ck of the metering**  **system before calibration was performed as shown in Figure 5.4 of EPA Method 5. The metering**  **systems's pump is operated for 5 minutes at an orifice manom eter setting of 0.5 inches H**  **2 0 to heat**  **up the pump and system to stabilize the meter inlet and outlet temperatures. Values for the orifice**  **setting (delta H), wet test meter volume (V w**  **), corresponding dry test meter volume (V d**  **), dry test meter inlet and outlet gas temperatures (t**  **di and t**  **dn ), and time are recorded for the initial calibration.**  **Then the ratio of the wet test meter to the dry test meter ( gamma) and the orifice pressure differential**  **that equates to 0.75 cfm at standard conditions (delta H@) are calculated. A post-test meter calibration was made on the dry gas meter**  **used during the test to check its accuracy against the pre-test calibration. This post-test**  **calibration check was made using the average orifice setting obtained during each test run and setting the vacuum**  **at the maximum value obtained during each test run. These test runs were made against DEECO'**  **s secondary reference dry gas meter which was calibrated against a wet test meter. The calib**  **ration data sheets for the dry gas meters are included in Appendix E.**  Thermocouples and Digital Indicators **- Thermocouples were calibrated by comparing them agai nst**  **an ASTM-3F mercury-in-glass thermometer at approximately 32** E **F (ice water), ambient temperature, and at approximately 220**  E **F. Each thermocouple was calibrated against temperature ra nges to which**  **it is typically exposed during test conditions, and they agreed within 1.5 percent (expressed in**  E **R) of the reference thermometer throughout the entire calibration ra**  **nge. Also, thermocouples were checked at ambient temperature at the test site to verify calibration. T**  **he calibration data sheets for the thermocouples are included in Appendix E.**  Pretest and Posttest Leak Checks of Sampling Trains **- Each Method 4 sampling train was subjected to pretest leak checks and posttest leak checks. For a**  **ll sampling runs the posttest leak checks were acceptable (less than 4% of the sampling rate a**  **t the highest vacuum recorded during the test run).**  4.2 Analytical QA/QC Results **Analytical measurements of precision and accuracy were made on stack gas samples, and are**  **summarized in a separate report.**